Perturbatively corrected ring-polymer instanton rate theory rigorously captures anharmonicity and deep tunneling

Abstract

In this paper, we derive a perturbatively-corrected instanton rate theory in the ring-polymer framework (RPI+PC), which significantly enhances the accuracy of instanton theory by using third and fourth derivatives of the potential to capture anharmonic effects. Instanton theory is a rigorous semiclassical method that extends transition-state theory by including quantum tunneling along a well-defined optimal tunneling pathway. However, the standard leading-order instanton theory (RPI) neglects anharmonicity perpendicular to this tunneling path. The RPI+PC method described here corrects this using only local information along the same instanton trajectory as the leading-order theory. Hence, RPI+PC does not require a global potential energy surface and is readily applicable in combination with ab initio electronic-structure methods. The derivation of the RPI+PC result is performed within the flux-correlation formalism using standard techniques from asymptotic analysis, and the final rate expression is shown to be independent of the choice of dividing surface. We demonstrate that RPI+PC represents a systematic improvement over RPI by analyzing its asymptotic properties in the semiclassical limit ($\hbar\to0$ with total thermal time $\tau^{\mathrm{tot}}=\beta\hbar$ kept constant) and illustrate its improved performance on a series of model systems for which exact results are available for comparison, including the collinear H+H$_2$ reaction and its isotopic variants.